EP1808917B1 - Method for producing manganese dry cell negative electrode zinc material - Google Patents

Method for producing manganese dry cell negative electrode zinc material Download PDF

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Publication number
EP1808917B1
EP1808917B1 EP05751594.2A EP05751594A EP1808917B1 EP 1808917 B1 EP1808917 B1 EP 1808917B1 EP 05751594 A EP05751594 A EP 05751594A EP 1808917 B1 EP1808917 B1 EP 1808917B1
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Prior art keywords
zinc
zinc alloy
sash
molded
rolling
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German (de)
English (en)
French (fr)
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EP1808917A4 (en
EP1808917A1 (en
Inventor
Mutsuhiro TOSHIBA BATTERY CO. LTD. MAEDA
Kazunari TOSHIBA BATTERY CO. LTD. KOBAYASHI
Yuk Fai ADVANCED ZONE LTD. LAU
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Toshiba Corp
Toshiba Lifestyle Products and Services Corp
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Toshiba Corp
Toshiba Lifestyle Products and Services Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0602—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a casting wheel and belt, e.g. Properzi-process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/1206—Accessories for subsequent treating or working cast stock in situ for plastic shaping of strands
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to methodology of manufacturing less-pollutive anode zinc material for manganese dry batteries, as compared to conventionally and currently available material, without using lead or adding it to zinc that is anode active material.
  • Lead deters cracks to run around the edges of a sheet in rolling ingot and on the wall of a can in forming the sheet.
  • lead is a metal element effective both in process-ability and corrosion resistance as an additive for anode zinc. And because of its vital role, it has been thought almost impossible to exclude lead from anode zinc material for manganese dry batteries. However, lead is an environmental hazardous material, and supply of anode zinc material without additive of lead is seriously demanded and development is actively conducted thereof.
  • the inventor conducted an experiment of the referenced technology by making an anode material and testing.through the manufacturing process generally done.
  • the process making a bar of ingot by casting melted zinc alloy with bismuth into a mold and cooling down; rolling the ingot by a rolling mill to a zinc sheet in a given thickness; and punching the sheet with a press machine to a circular or hexagonal pellet to form a finished can.
  • a can was made out anyhow; but progress of cooling was too slow and irregular or large rough crystals grew in the zinc sheet, which caused cracks around the rims of the zinc sheet; so material yield was quite poor and possible high rate of No Good' mixed in finished cans was feared for mass production.
  • the bismuth-added ingot could not be processed by a continuous casting and rolling system, which is the system for the lead-added ingot, because of breakage of molded sheets joining one another in sash during extrusion and cracks at both sides before and after entering into the rolling mill.
  • the range of processing parameters is narrower and optimization of manufacturing is extremely difficult for bismuth-added ingot, as compared for lead-added one.
  • no example of successful manufacturing a zinc sheet exists from bismuth-added active anode material until today.
  • JP 7 296 813 relates to zinc can anodes for batteries.
  • the anodes are made of a zinc alloy which comprises bismuth and calcium, but no appreciable amounts of toxic materials such as lead, cadmium and mercury, and are said to have good corrosion resistance and mechanical strength.
  • JP 2003 502499 and WO 0077868 describe a method of preparing a foil of an alloy of zinc with at least one additive metal, which may be selected from bismuth, indium and calcium, optionally together with aluminium.
  • the foil is said to be bendable through small bend radii without cracking, therefore allowing the use as electrode material for batteries, in particular spiral-wound electrodes for jelly roll batteries.
  • the present invention relates to method for manufacturing non lead added anode zinc material for manganese dry batteries, which comprises the steps at least of:
  • the present invention relates to method for manufacturing non lead added anode zinc material for manganese dry batteries, which comprises the steps at least of:
  • the present invention relates to method for manufacturing non lead added anode zinc material for manganese dry batteries, which comprises the steps at least of:
  • Breakage of a zinc sheet during process from casting .to rolling is due to large, irregular or rough crystals which bismuth precipitates into the crystalline structure and growing acicular crystals, whereas that is not a case with lead-additive; no growing acicular crystals, the crystalline structure keeping evenly scattered minute crystals.
  • This Invention was made to solve the problems involved in manufacturing anode zinc material without adding lead and aims to present a method of manufacturing practicable and defect-less non-lead-added zinc alloy and sheets.
  • the first phase of this Invention is a method of manufacturing a non-lead-added manganese dry battery which method contains at least an alloy compounding process to make a lot of zinc alloy by melting in a melting furnace the material containing zinc with addition of bismuth by 0.1 mass % to 0.7 mass % and other elements of inevitably accompanied impurities in zinc; and A casting process to make a molded material from the melted alloy with a casting machine; and a rolling process to roll the sheet; and A punching process to punch circular or hexagonal pellets out of the rolled sheet.
  • the second phase of this Invention is a method of making ingot with individual molds by natural cooling of the cast zinc alloy and method of subsequent processes to make anode zinc material for manganese dry batteries.
  • Productivity can be increased by rapid solidification of the melted alloy, cooling by water surrounding the mold, whereby crystals become minute preventing from cracks of a zinc sheet in rolling and also providing a number of molds enabling non-stop cooling process. But preferable is rolling the ingot in 2 or 6 times.
  • This Invention materializes a casting and rolling method to enable manufacturing a crack-less and breakage-free stable and reliable quality of non-lead-added anode zinc for a manganese dry battery and realizes supply of inexpensive and environment friendly anode zinc material for manganese dry batteries.
  • the manufacturing method is comprised of an alloy compounding process to compound zinc alloy in a melting furnace, a casting process to mold melted alloy, a rolling process to roll the molded alloy ingot to a zinc sheet with a rolling machine, and a press process to punch the zinc sheet to pellets in such shapes as circle, hexagon, or quadrilateral, of which 4 corners are chamfered, for quadrilateral laminated manganese dry batteries 6F22 of JIS standard as shown in the Fig. 4 or cylindrical dry batteries in the Fig.3 .
  • the Fig.1 shows the casting system for embodying this Invention.
  • the Fig.7 shows an enlarged image of the key area of the casting system.
  • the area of this system for casting molten zinc alloy consists of the melting furnace marked 11, an outlet marked 12 to take the molten alloy out of the furnace, a mold marked 13 to guide and feed the molten alloy from the outlet to a groove marked 14c made on a peripherally of a rotate-able disc marked 14.
  • the mold 13 is incorporated with molten guiding and molding parts, called side dams marked 13a and 13b with a bottom cover (not shown in the drawing).
  • the side dams and the bottom are positioned to contact the peripherally 14c and a side wall (14d) as they rotate as the disc does, and the molten alloy is fed to the groove (14c) of the disc (13) and is cast there.
  • Important is heat control of the casting process, and desirable is to control heat with equipment for heating, cooling, and measuring temperature. (The equipment is not described in the drawing.)
  • Contacting the disc (14) three pulleys (15a) (15b) and (15c) are arranged, and a heat-resistant belt (16) is stretched over the pulleys.
  • the molten alloy zinc is cooled in the space formed by the disc's groove (14c) and the belt (16), and becomes molded material in sash state. Then the material is rolled by a single or numbers of roller 19 to a zinc sheet marked 20 in a specified thickness for punching process to designated shapes of pellets as marked 21.
  • First compound zinc alloy by adding bismuth to pure zinc and melt in the melting furnace 11.
  • the amount of bismuth is to be 0.1 to 0.7 mass % of the compounded alloy.
  • Preferable amount of magnesium to add is to be more than 0.0005 mass % and less than 0.05 mass % of the alloy composition. That hardens anode zinc material and makes its crystals minute for casting, thereby preventing from breakage of the sash- state molded alloy at the exit of the casting system and from cracks in the rolling process. But excessive addition of magnesium is not desirable, for it makes undesirable Vicker's hardness of the zinc sheet for bad process-ability in making cans. It is in this process that lead added to zinc alloy effects favorably for mold-ability.
  • This Invention rejects lead as additive for environmental consideration, while it does not exclude lead as an inevitable impurity contained in the zinc alloy accompanied with zinc ground metal. Likewise impurities such as Fe, Cu, Cd, Sn, A1, and other elements do not matter for this Invention as far as they are contained in a level of amount of inevitable impurities.
  • the molten zinc alloy made in the previous process is fed to the mold (13) from the outlet (12) of the melting furnace (13) and is molded to a sash-state material by the rotating casting disc.
  • the casting system is provided with the rotating disc (14), a circular rotating component which can be cooled by water and has a groove on the rim.
  • pulleys (15a), (15b), and (15c) are provided, and the heat-resistant belt (16) like a steel belt is stretched over three pulleys. This belt (16) moves toward same direction in the same speed as the disc (14) rotates.
  • the molten zinc alloy is filled in the disc's groove and cooled to the molded sash-state material in the space formed by the belt and the disc groove.
  • More than 400 °C and less than 600 °C is a preferable range of temperature of the molten zinc alloy when it is fed from the melting furnace's (11) outlet (12) to the disc (14). If the temperature is out of that range, obtainable molded sash-state material tends to break. And preferable is rapid solidification of the disc (14) to cool molten zinc alloy thereon for minuteness of the crystals.
  • Water cooling can be applied to rapid solidification of the disc (14). That is done by incorporating a water-way inside the disc (14), and cooling by pouring water below 40 °C at water pressure about 0.2 MPa into the disc.
  • Adoption of those process conditions suppresses acicular crystals to take place and grow in the molded sash-like material, whereby breakage and cracks are prevented in the subsequent processes.
  • the thickness of a molded sash-like material is decided by the depth of the groove on the periphery rim of the disc(14).
  • a thin molded sash is less breakable and easy for handling. But there is a limit for thinness, since property of an anode zinc material to be completed is restricted and defined by mechanical strength and electric potential of a battery to be made out. Thinning the molded sash excessively results in lowering compression rate in the rolling process, and the quality of a sheet after rolling may be not good for voids within the sheet.
  • This thickness for molding sash is set up according to the thickness of zinc pellets to be punched out and compression rate of sash thickness and pellet thickness.
  • diameter of the rotating disc (14) is preferably to be more than 200 cm.
  • diameter of the disc (14) is 20 to 200 cm.
  • acicular crystals of the zinc alloy are found epitaxial orthogonally to the direction of length of the molded sash. Those acicular crystals are supposed to emerge as cooling of interior area of the sash tends to delay than the upper and the lower surface, while the sash is cooled from the upper and the lower faces. If many acicular crystals take place, the molded sash becomes breakable and tends to get cracked in the subsequent rolling process.
  • the acicular crystals as called in this Invention refers to those crystals epitaxial anisotropically, which are located in the Fig.5 and the Fig.6 .
  • the Fig.5 shows cross section of the sash as being cut vertically to the length direction, which cross section contains acicular crystals.
  • the Fig.6 is the picture of a cross section of a sash which crystal structure contains almost no acicular crystals.
  • those crystals are meant herein to be of not necessarily a perfect crystal structure, but also of one axis anisotropical crystal structure and of an imperfect crystal structure with anisotropy.
  • the cross section was the face of the zinc sheet or strip being cut or grinded to an optional direction, and the surface observed was an area with average or typically common crystal structure of the relevant cross section.
  • the molded sash-like material made in the preceded process is conveyed to the rolling process by a guide roller marked 18.
  • the rolling system consists of at least 2 pairs of twin roller 19-1a, b and 19-2a, b.
  • the molded sash is rolled under an adequate pressure, and a zinc alloy sheet is made out. Thickness of the sheet is decided depending on the type and the size of dry battery to fabricate, and thickness for zinc pellets for zinc cans is normally set in a range of 4 to 7 mm.
  • Preferable compression rate thickness of a sheet after rolling to thickness of the molded sash before rolling
  • Preferable compression rate is in a range more than 30 %.
  • the compression rate lower than that range, voids conceived in the interior of the molded sash remain after the rolling process and deteriorates quality of the pellets.
  • Composition of the alloy of this Invention more likely causes cracks at the side edges of the rolled sheet than that of the lead-added alloy does, and intensive compression for once is not desirable for deterioration of the metal structure of the rolled sheet incurring some problems.
  • desirable is rolling for 2 times and is to reduce compression rate for 1 time of rolling. However rolling in more than 6 times reduces the temperature of material surface, which incites cracks and should be avoided.
  • a zinc sheet marked 20 in Fig.1 made by the rolling process is punched to quadrilateral, which 4 corners to be chamfered, circular or hexagonal pellets with a press machine marked 21.
  • the pellets are used for anode zinc plates for 6F22 batteries or anode zinc cans with bottom cover for cylindrical manganese dry batteries by deep-drawing.
  • the batteries are fabricated by assembling those plates or cans together with other parts such as cathodes, positive electrodes and current collectors.
  • a press machine generally known can be used.
  • the system consist of an abutment, a die in a designated shape for fixed onto the abutment, a tap fit into the depressed inner part of the die, and a driving device to thrust the tap into the die and draw out.
  • a zinc alloy sheet is placed in the gap between the die and the tap, and is punched by driving the tap. Normally a die and a tap are replaceable, and suitable pair of die and tap are installed to punch the sheet to a required shape.
  • the compounded and melted zinc alloy in the melting furnace is molded to sash-like molded material, which is rolle formed by the rollers 19-1a, b and 19-2a, b to the zinc sheet (20) in a required thickness.
  • the sheet (20) is wound to a roll of a specified diameter. Subsequently the sheet is rewound and is punched to anode zinc pellets.
  • the sash-like molded material can be cut to a specified length, and fed to subsequent process in a form of zinc strip. Also possible is to cut the sheet after the casting and the rolling processes, and fed to the punching process. By these methods, the casting, the rolling, and the punching processes are detached at one or some junctures, whereby flexibility of the manufacturing process is enhanced for better workability.
  • each mold is pour filled with the molten zinc alloy, which mold with molten in it is dipped into a water tank with cooling water below 40 °C, whereby the molten is rapidly cooled and solidified.
  • sheet (s) which sheet is punched or then deep-drawn to be zinc plates or zinc cans for manganese dry batteries.
  • Alloy composition 100 kg pure zinc and different additives for the embodiment examples 1 to 9 and the comparative examples 1 and 2 as indicated in the Table 1 herein below.
  • Manufacturing system as of Drawing 2 equipped with 100 cm diameter disc.
  • R20 manganese dry batteries were fabricated using above-mentioned zinc pellets and evaluation was done on the batteries.
  • First cathode compound was prepared by dry mixing of cathode active material, manganese dioxide for major ingredient, and acetylene black for conductive material, followed by spraying electrolyte to the compound and wet mixing thereof.
  • Crimp seal whole can with the medium of a insulating ring. That completes a manganese dry battery.
  • the batteries were discharged with a load of 40 ohm ( ⁇ ) for 4 hours a day in a room temperature. Subsequently evaluated was life characteristic at the time of 0.9 V, and obtained was relative values to 100 the standard representing the characteristic of conventional and currently available batteries. The number of the samples was 9 of R20 made in this work.
  • Cutting test samples (a piece 0.3 mm thick 10.0 mm width, 50.0 mm length)out of the zinc cans, the samples were polished at their surface and cross section to mirror face status with the sand papers #400, #600, #800, #1000 and #1200, and were degreased in an Ultrasonic Cleaner.
  • the liquid used was of 10 mass % of NaOH and water.
  • the degreased sample was weighed in 0.1 mg accuracy and then dipped into electrolyte in a constant temperature water tank. Weight decrease of the sample after 66 hours in 45 °C was taken for decrease by corrosion or corrosion-decrease.
  • the zinc pellets by the manufacturing method of this Invention have competent corrosion-resistance and life characteristic and are useable enough for batteries in mass production. And, the embodiment examples had very few cracks endorsing superior process-ability of the zinc alloy material by the manufacturing method of this Invention.
  • preferable amount of bismuth to add is more than 0.1 mass % and less than 0.7 mass %; magnesium more than 0.0005% and less than 0.05 mass %.
  • Magnesium additive less than 0.0005% is undesirable for shortage of mechanical strength (hardness) of a zinc can or pellets; more than 0.05 mass % is also undesirable for increase of corrosion-decrease, through that may be still in a tolerable range, and for decrease of relative life value.
  • Zinc sheet manufacturing test was conducted by using manufacturing system equipped with 100 cm diameter disc as of Fig. 2 varying alloy composition with constant casting and rolling condition as shown below. Appearance and cross sectional crystal condition of the manufactured zinc sheets were checked..Results are shown in Table 2.
  • a result of checking cracks in the zinc sheet after rolling was classified to 4 levels of excellent, good, pass, and failure according to the following criteria.
  • Rolling is preferably to be done for plural number of times; 4 times of rolling to a given thickness gave a good result in crystal condition with very few cracks; 6 times or more of rolling turned out not very desirable as the material temperature dropped and the crystals became rough and large causing cracks.
  • Sash-state materials were manufactured using manufacturing system as of Fig 2 from zinc alloy prepared by adding 0.3 mass % bismuth to 100 kg pure zinc. Casting machine disc diameter was varied under casting condition shown in Table 6. Finally, appearance and cross sectional crystal condition of the manufactured sash-state materials and zinc sheets were checked. Concerning thickness of molded sash-state material, the thinner it is, the better it is for flexibility not easily breakable, however, compression ratio must be counted at least 30 % for the rolling process and the thinness is limited by the thickness of zinc pellets to be punched out of a zinc sheet after rolling.
  • the molded material in sash-state is thick, it may happen that the material breaks around the exit of the casting machine, and in this case it is advisable to use a disc of large diameter and to arrange the material so as it may not curve very much in coming out of the disc in cooled and semi-solidified status and laying flat on the conveyor.
  • the test outcome was as follows.
  • a suitable diameter of a casting machine disc is in a range from 20 to 200 cm, depending on the thickness of the molded sash-state zinc material.
  • Table 6 Molded sash-state material thickness (mm) Casting machine disc diameter (cm) Breakage of zinc sash at casting machine exit (%) Crystal condition of zinc sash at casting machine exit (rate of acicular crystal) (%) Crack of zinc sheet after rolling (excellent, good, pass, failure Embodiment example 34 1 18 0 11 pass Embodiment example 35 1 25 0 7 good Embodiment example 36 1 50 0 4 excellent Embodiment example 37 1 100 0 8 good Embodiment example 38 1 200 0 9 good Embodiment example 39 10 18 15 14 pass Embodiment example 40 10 50 0 6 excellent Embodiment example 41 10 100 0 5 excellent Embodiment example 42 10 200 0 8 good Embodiment example 43 10 220 0 13 pass Embodiment example 44 30 18 10 14 pass Embodiment example 45 30 50 0
  • Embodiment example 49 to 53 Zinc alloy was prepared adding 0.3 mass % bismuth to 100kg pure zinc. Experiments were conducted using manufacturing system as of Fig 2 with condition shown below.
  • average crystal grain diameter is preferable to be less than 75 ⁇ m in a zinc alloy sheet after rolling, and that the cross section square measure containing crystals of average grain diameter more than 200 ⁇ m preferably should share less than 10 % of an optional cross section square measure of a zinc sheet.

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EP05751594.2A 2004-10-15 2005-06-06 Method for producing manganese dry cell negative electrode zinc material Active EP1808917B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004301215 2004-10-15
PCT/JP2005/010378 WO2006040857A1 (ja) 2004-10-15 2005-06-06 マンガン乾電池負極亜鉛材料の製造方法

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EP1808917A1 EP1808917A1 (en) 2007-07-18
EP1808917A4 EP1808917A4 (en) 2008-01-16
EP1808917B1 true EP1808917B1 (en) 2016-03-30

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US (1) US7874346B2 (zh)
EP (1) EP1808917B1 (zh)
JP (1) JP5072363B2 (zh)
KR (1) KR100929283B1 (zh)
CN (1) CN100530775C (zh)
HK (1) HK1110152A1 (zh)
PL (1) PL1808917T3 (zh)
WO (1) WO2006040857A1 (zh)

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CN101383410A (zh) * 2003-12-25 2009-03-11 东芝电池株式会社 锰干电池
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KR101500643B1 (ko) * 2007-05-10 2015-03-10 재단법인 포항산업과학연구원 연속 성형 장치 및 연속 성형 방법
CN103480811B (zh) * 2013-10-12 2015-07-01 武汉钢铁(集团)公司 急冷制带的设备及工艺
PL3624963T3 (pl) 2017-05-19 2022-01-31 Iq Power Licensing Ag Urządzenie do odlewania nośników elektrod do akumulatorów kwasowo-ołowiowych
EP3862446A4 (en) 2018-10-03 2021-11-03 Mitsui Mining & Smelting Co., Ltd. ZINC FOIL, ACTIVE MATERIAL OF NEGATIVE ELECTRODE OF A PRIMARY BATTERY THEREOF AND METHOD FOR MANUFACTURING ZINC FOIL
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JP7081056B2 (ja) 2020-03-27 2022-06-06 三井金属鉱業株式会社 亜鉛箔及びこれを用いた電池用負極活物質材料、並びに亜鉛箔の製造方法
CN111570737B (zh) * 2020-06-23 2024-06-18 涿州北方重工设备设计有限公司 浇铸机
CN112371847A (zh) * 2020-10-23 2021-02-19 昆山智盛精密铸造有限公司 一种高散热性合金笔记本电脑壳体成型模具及生产方法

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JP5072363B2 (ja) 2012-11-14
EP1808917A4 (en) 2008-01-16
JPWO2006040857A1 (ja) 2008-05-15
HK1110152A1 (en) 2008-07-04
US20080029189A1 (en) 2008-02-07
PL1808917T3 (pl) 2016-09-30
CN101080829A (zh) 2007-11-28
WO2006040857A1 (ja) 2006-04-20
CN100530775C (zh) 2009-08-19
EP1808917A1 (en) 2007-07-18
US7874346B2 (en) 2011-01-25
KR20070083911A (ko) 2007-08-24

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